Softening silicone formulations for textile finishing

ABSTRACT

The invention concerns novel formulations containing at least one quaternized aminoalkylsiloxane and at least one compound selected among: a) non-ionic hydrophilic surfactant compounds, b) hydrophilic dispersants and c) divalent of trivalent metal salts with inorganic acids. Said formulations are excellent textile softeners for finishing textile structures in accordance with continuous or drawing process and are characterized by particular shearing stability.

The invention relates to novel formulations based on quaternizedaminoalkylsilicones or -siloxanes, to processes for preparing theseformulations and to their use as textile assistants for finishingtextile materials.

Silicone softeners are used widely for the finishing of textilematerials. For the practical use of the silicone softener emulsions,requirements such as storage stability, thermal stability, resistancetoward whiteners and other anionic textile assistants, resistance to pHchanges and salt addition and against the action of mechanical energyare of central significance. Particularly the stability against theaction of mechanical energy, the shear stability or jet stability, oftenpresents silicone softener emulsions with great difficulties underindustrial conditions (cf. R. Zyschka, Melliand Textilberichte June2001, 497).

Microemulsions offer the fundamental advantage of thermodynamicstability. In a multitude of publications, the equilibrium phasebehavior is treated as a function of the structure of the oil to beemulsified and/or of the surfactant(s). Likewise systematically studiedhas been the addition of inorganic salts (cf. M. Kahlweit et al.,Langmuir 11[1995], 3382; M. Kahlweit et al., Langmuir 11[1995]). Theequilibrium phase behavior of microemulsions of low molecular weightsilicones has likewise been investigated (EP-A 774482; H. von Berlepschet al, Progr. Colloid Polymer Science 111[1998], 107).

With regard to the softening components, combinations ofhydrocarbon-based quats with silicone quats (GB-A 1549180) or elsesilicone polyethers with silicone quats (U.S. Pat. No. 4,921,895) havebeen proposed.

To improve the hydrophilicity, the widely utilized aminoalkylsiloxanesare increasingly being replaced by polyether-modified aminoalkylsiloxaneoils (cf. EP-A 578144).

An additional introduction of alkoxysilyl structures into polyether- andamino-substituted silicones has likewise been proposed (US-A20020028900).

Finally, true permanently hydrophilic textile softeners based onsilicone quats have been disclosed in WO 02/10256, WO 02/10257 and WO02/10259.

Fine microemulsions of aminoalkylsiloxanes are said to be obtainable ina two-stage process by preparing a concentrate of aminoalkylsiloxane,silicone-insoluble surfactant and a little water with subsequent rapidstirring into water (U.S. Pat. No. 4,620,878).

According to DE-A 3723697, aminosiloxane emulsions are said to becomemechanically stable as a result of the use of water-soluble nonionogenicemulsifiers. For extreme shear stresses, as are achieved on modern jetplants, it has been found that the inventions disclosed in DE-A 3723697are insufficient to prevent deposits in the jet plant and on thetextiles to be treated.

According to WO 02/10501, aminofunctional organosilicon compounds aresaid to become mechanically stable even in jet dyeing machines withoutusing water-soluble nonionogenic emulsifiers. It has been found that theinventions disclosed in WO 02/10501 are likewise not yet sufficient toreliably prevent deposits on differently pretreated textiles.

Mechanical stability of aminosiloxane microemulsions is also said to beachievable by using betaines, optionally in combination withnonionogenic surfactants of the HLB range from 5 to 16 (cf. U.S. Pat.No. 5,573,694; U.S. Pat. No. 5,520,827).

It is known in dyeing technology that complex mixtures which comprisesulfonated alkylnaphthyl derivatives and halogenated hydrocarbons can beutilized as jet-stable dyeing accelerator formulations (U.S. Pat. No.4,080,166).

Such sulfonated naphthyl derivatives in combination with fatty alcoholethoxylates have also been proposed for the stabilization of inkjetableformulations (U.S. Pat. No. 6,302,948). The combination of fatty alcoholethoxylates with pigments of a certain size is likewise said to lead toinkjetable systems (U.S. Pat. No. 6,099,627).

Finally, it is also known that salts of strong acids, e.g. Al₂(SO4)₃×18H₂O ensure protonation of cationic dyes in thermal transfer printingpastes but simultaneously impair their stability (cf. U.S. Pat. No.5,925,701).

It is common to all of the proposals cited that they do not contain anyhints to measures by which emulsions or microemulsions of silicone-basedtextile softeners, preferably aminosiloxanes and quaternizedaminoalkylsiloxanes (silicone quats) can be stabilized reliably againstthe action of high mechanical energy input of the modern jet systems incombination with greatly varying liquor ratios and the influence ofvarying pretreatment preparations on the fibers. Moreover, the prior artdoes not disclose any measures by which the simultaneously occurringhigh foaming tendency (causes stain formation) of textile softenerformulations under high mechanical energy input can be restricted.

It is thus an object of the present invention to describe measures bywhich emulsions or microemulsions of silicon-based textile softeners,preferably quaternized aminoalkylsiloxanes (silicone quats), can bereliably stabilized under the action of high energy input (extremelyhigh shear forces in modern jet systems) in combination with greatlyvarying liquor ratios, and the influence of varying pretreatmentpreparations and the foaming tendency can be simultaneously restricted.

It has been found that, surprisingly, this object is achieved by thecombination of quaternized aminoalkylsiloxanes with highly hydrophilicnonionogenic interface-active compounds (surfactants) and/or highlyhydrophilic dispersants and/or salts of polyvalent cations andoptionally further customary formulation agents.

The present invention therefore relates to formulations comprising atleast one quaternized aminoalkylsiloxane and at least one compound fromthe group of

-   -   a) the hydrophilic, nonionogenic, interface-active compounds,    -   b) the hydrophilic dispersants and    -   c) the salts of di- or trivalent metals with inorganic acids.

Preferred hydrophilic, nonionogenic, interface-active compounds (a) inthe context of the invention are substances which lower the surfacetension of water to below 45 mN/m. They are in particular compoundsmodified with ethylene/propylene oxide (EO/PO), optionally unsaturatedand/or branched, from the group of the fatty alcohols, fatty acids,alcohols, acids, alkylaryl derivatives, fatty amines, glycerides andsorbitan esters, in each of which the number of EO/PO units is between15 and 150, the ratio of PO units to EO units being equal to 0.25 orlower than 0.25, and in each of which the number of ethylene oxide units(EO fraction) is greater than or equal to the number of carbon atoms inthe non-EO fraction, or are alkyl-polyglycosides, ethyleneoxide/propylene oxide copolymers and polyethersiloxanes.

Hydrophilic dispersants (b) in the context of the invention aresubstances which, when added to water, lower the surface tension to avalue between 72 to 45 mN/m.

The preferred compounds (b) are water-soluble polysaccharides such ascarboxy-methylcellulose, hydroxyethylcellulose,methylhydroxypropylcellulose or compounds of the formula

-   -   where    -   x is from 1.5 to 20, preferably from 1.5 to 10.

The salts (c) are metal salts having a valency of two or higher,preferably calcium, magnesium and aluminum salts, optionally in the formof their hydrates, with inorganic acids such as hydrochloric acid,sulfuric acid, phosphoric acid. The counterions are to be selected insuch a way that sufficient water and formulation solubility is ensuredat a given stability of the salt. Examples of such salts are Ca(Cl)₂,Mg(Cl)₂ and Al₂(SO₄)₃, optionally in the form of their hydrates.Specifically, the compounds (a) are those of the formulae

-   -   where    -   E is an R¹ radical, hydrogen, straight-chain or branched,        saturated or mono- or polyunsaturated C₁-C₁₈-alkyl which is        optionally mono- or polysubstituted by —OH, C₁-C₄-alkoxy,        C₁-C₄-alkoxycarbonyl or carbonyl, or is C₅-C₁₀-cyclo-alkyl which        is optionally mono- or polysubstituted by C₁-C₄-alkyl, —OH,        C₁-C₄-alkoxy, C₁-C₄-alkoxycarbonyl or carbonyl    -   R¹ is straight-chain or branched, saturated or unsaturated        C₈-C₄₀-alkyl whose alkyl chain is optionally interrupted singly        or multiply by oxygen and/or nitrogen atoms and which is        optionally mono- or polysubstituted by —OH, C₁-C₄-alkoxy,        C₁-C₄-alkoxycarbonyl or carbonyl, amino, mono- or        di-C₁-C₄-alkylamino, or is C₅-C₁₀-cycloalkyl whose alkyl chain        is optionally interrupted singly or multiply by oxygen and/or        nitrogen atoms and which is optionally mono- or polysubstituted        by C₁-C₄-alkyl, —OH, C₁-C₄-alkoxy, C₁-C₄-alkoxycarbonyl or        carbonyl, amino, mono- or di-C₁-C₄-alkylamino,    -   R² is straight-chain or branched, saturated or mono- to        polyunsaturated C₈-C₄₀-alkyl which is optionally mono- or        polysubstituted by —OH, C₁-C₄-alkoxy, C₁-C₄-alkoxycarbonyl or        carbonyl,    -   R³ is straight-chain or branched C₁-C₂₆-alkyl or C₆-C₁₀-aryl,        —CH₂CH₂—O—[CH₂CH₂O]_(q)—[CH₂CH(CH₃)O]_(r)-E,        —CH₂CH₂CH₂—O—[CH₂CH₂O]_(q)—[CH₂CH(CH₃)O]_(r)-E        —CH₂CH₂CH₂—O—CH₂CHOHCH₂—O—[CH₂CH₂O]_(q)—[CH₂CH(CH₃)O]_(r)-E        —Z—[CH₂CH₂O]_(q)—[CH₂CH(CH₃)O]_(r)-E        -   where        -   Z is a straight-chain or branched alkyl or cycloalkyl            radical which is in each case interrupted by —O— and/or —CO—            and may optionally be substituted by at least one OH group,        -   or        -   q is from 15 to 150,        -   q1 and q2 are each independently from 0 to 150,        -   where the sum of q1+q2=q,        -   q3, q4, q5 and q6 are each independently from 0 to 150        -   where the sum of q3+q4+q5+q6=q,        -   r is from 0 to 50,        -   r1 and r2 are each independently from 0 to 50        -   where the sum of r1+r2=r,        -   r3, r4, r5 and r6 are each independently from 0 to 50        -   where the sum of r3+r4+r5+r6=r, and        -   the ratio of r:q≦0.25,        -   m is from 1 to 50,        -   m7 and m8 are each independently from 1 to 50        -   where 2≦m7+m8 and the sum of m7+m8=m+1, and        -   the ratio of q:m ≧4,        -   s is from 5 to 150,        -   t is from 5 to 150        -   where 0.05≦s:t≦20,        -   0≦z1≦2000,        -   at least one R4≠R3, and        -   0.01≦Σ alkyl radicals R³:Σ q+r≦1.

Specifically, the compounds (a) are also those of the formulae (1′) to(9′)

-   -   where    -   the brackets “{” and “}” shown in formulae (1′)-(8′) mean that        the ethylene oxide or propylene oxide units within these        brackets may either be arranged blockwise as shown or else be in        any random distribution,    -   E is an R¹ radical, hydrogen, straight-chain or branched,        saturated or mono- or polyunsaturated C₁-C₁₈-alkyl which is        optionally mono- or polysubstituted by —OH, C₁-C₄-alkoxy,        C₁-C₄-alkoxycarbonyl or carbonyl, or is C₅-C₁₀-cyclo-alkyl which        is optionally mono- or polysubstituted by C₁-C₄-alkyl, —OH,        C₁-C₄-alkoxy, C₁-C₄-alkoxycarbonyl or carbonyl,    -   R¹ is straight-chain or branched, saturated or unsaturated        C₈-C₄₀-alkyl whose alkyl chain is optionally interrupted singly        or multiply by oxygen and/or nitrogen atoms and which is        optionally mono- or polysubstituted by —OH, C₁-C₄-alkoxy,        C₁-C₄-alkoxycarbonyl or carbonyl, amino, mono- or        di-C₁-C₄-alkylamino, or is C₅-C₁₀-cycloalkyl whose alkyl chain        is optionally interrupted singly or multiply by oxygen and/or        nitrogen atoms and which is optionally mono- or polysubstituted        by C₁-C₄-alkyl, —OH, C₁-C₄-alkoxy, C₁-C₄-alkoxycarbonyl or        carbonyl, amino, mono- or di-C₁-C₄-alkylamino, or is C₆-C₁₀-aryl        which is optionally substituted, especially by C₃-C₁₅-alkyl,    -   R² is straight-chain or branched, saturated or mono- to        polyunsaturated C₈-C₄₀-alkyl which is optionally mono- or        polysubstituted by —OH, C₁-C₄-alkoxy, C₁-C₄-alkoxycarbonyl or        carbonyl,    -   R³ is straight-chain or branched C₁-C₂₆-alkyl or C₆-C₁₀-aryl,    -   R⁴ is R³ or is a radical of the formulae        -   where        -   Z is a straight-chain or branched alkyl or cycloalkyl            radical which is in each case interrupted by —O— and /or            —CO— and may optionally be substituted by at least one OH            group        -   or        -   where the brackets “{” and “}” shown in the aforementioned            formulae again mean that the ethylene oxide or propylene            oxide units within these brackets may either be arranged            blockwise as shown or else may be in any random            distribution,        -   q is from 15 to 150,        -   q1 and q2 are each independently from 0 to 150        -   where the sum of q1+q2=q,        -   q3, q4, q5 and q6 are each independently from 0 to 150        -   where the sum of q3+q4+q5+q6=q,        -   r is from 0 to 50,        -   r1 and r2 are each independently from 0 to 50        -   where the sum of r1+r2=r,        -   where the sum of r3+r4+r5+r6=r, and        -   the ratio of r:q≦0.25,        -   m is from 1 to 50,        -   m7 and m8 are each independently from 1 to 50        -   where 2≦m7+m8 and        -   the ratio of q:m≧4,        -   s is from 5 to 150, preferably 15-150,        -   t is from 5 to 150, preferably from 5 to 150 and in            particular from 5 to 20,        -   where t:s≦0.25        -   0≦z1≦2000,        -   0≦z2≦2000,        -   at least one R4≠R3, and        -   for formula (9′):            0.01≦Σ alkyl radicals R³ :Σ q+r≦1.

In particular, the compounds (a) are those of the formulae (1) to (9)where

-   -   E is hydrogen, straight-chain or branched, saturated or mono- or        polyunsaturated C₁-C₄-alkyl which is optionally mono- to        disubstituted by —OH, C₁-C₄-alkoxy, C₁-C₄-alkoxycarbonyl or        carbonyl, or is C₅-C₆ -cycloalkyl which is in each case        optionally mono- or polysubstituted by C₁-C₄-alkyl, —OH,        C₁-C₄-alkoxy, C₁-C₄-alkoxycarbonyl or carbonyl,    -   R¹ is straight-chain or branched, saturated or unsaturated        C₁₀-C₃₆-alkyl whose alkyl chain is optionally interrupted singly        or multiply by oxygen and/or nitrogen atoms and which is        optionally mono- or polysubstituted by —OH, C₁-C₄-alkoxy,        C₁-C₄-alkoxycarbonyl or carbonyl, amino, mono- or        di-C₁-C₄-alkylamino, or is C₅-C₆-cycloalkyl whose alkyl chain is        optionally interrupted singly or multiply by oxygen and/or        nitrogen atoms and which is optionally mono- or polysubstituted        by C₁-C₄-alkyl, —OH, C₁-C₄-alkoxy, C₁-C₄-alkoxycarbonyl or        carbonyl, amino, mono- or di-C₁-C₄-alkylamino,    -   R² is straight-chain or branched, saturated or mono- to        polyunsaturated C₁₀-C₃₆-alkyl which is optionally mono- or        polysubstituted by —OH, C₁-C₄-alkoxy, C₁-C₄-alkoxycarbonyl or        carbonyl,    -   R³ is straight-chain or branched C₁-C₁₈-alkyl or C₆-C₁₀-aryl,    -   R⁴ is an R³ radical or is a radical of the formulae        -   or            —CH₂CH₂CH₂—O—[CH₂CH₂O]_(q)—[CH₂CH(CH₃)O]_(r)-E,        -   q is from 20 to 100,        -   q1 and q2 are each independently from 20 to 100        -   where the sum of q1+q2=q,        -   q3, q4, q5 and q6 are each independently from 20 to 100        -   where the sum of q3+q4+q5+q6=q,        -   r is from 0 to 20,        -   r1 and r2 are each independently from 0 to 20        -   where the sum of r1+r2=r,        -   r3, r4, r5 and r6 are each independently from 0 to 20        -   where the sum of r3+r4+r5+r6=r, and        -   the ratio of r:q≦0.25,        -   m is from 1 to 7,        -   m7 and m8 are each independently from 1 to 7        -   where 2≦m7+m8 and the sum of m7+m8=m+1, and        -   the ratio of q:m≧4,        -   s is from 5 to 100,        -   t is from 5 to 100        -   where0.05≦s:t≦20,        -   0≦z1≦2000,        -   0≦z2≦2000,        -   at least one R4≠R3, and        -   and        -   0.01≦Σ alkyl radicals R³:Σ q+r≦0.5.

In particular, the compounds (a) are those of the formulae (1′) to (9′)where

-   -   E is hydrogen, straight-chain or branched, saturated or mono- or        polyunsaturated C₁-C₄-alkyl which is optionally mono- to        disubstituted by —OH, C₁-C₄-alkoxy, C₁-C₄-alkoxycarbonyl or        carbonyl, or is C₅-C₆ -cycloalkyl which is in each case        optionally mono- or polysubstituted by C₁-C₄-alkyl, —OH,        C₁-C₄-alkoxy, C₁-C₄-alkoxycarbonyl or carbonyl,    -   R¹ is straight-chain or branched, saturated or unsaturated        C₁₀-C₃₆-alkyl whose alkyl chain is optionally interrupted singly        or multiply by oxygen and/or nitrogen atoms and which is        optionally mono- or polysubstituted by —OH, C₁-C₄-alkoxy,        C₁-C₄-alkoxycarbonyl or carbonyl, amino, mono- or        di-C₁-C₄-alkylamino, or is C₅-C₆-cycloalkyl whose alkyl chain is        optionally interrupted singly or multiply by oxygen and/or        nitrogen atoms and which is optionally mono- or polysubstituted        by C₁-C₄-alkyl, —OH, C₁-C₄-alkoxy, C₁-C₄-alkoxycarbonyl or        carbonyl, amino, mono- or di-C₁-C₄-alkylamino, or is C₆-C₁₀-aryl        which is optionally substituted, especially by C₃-C₁₅-alkyl,    -   R² is straight-chain or branched, saturated or mono- to        polyunsaturated C₁₀-C₃₆-alkyl which is optionally mono- or        polysubstituted by —OH, C₁-C₄-alkoxy, C₁-C₄-alkoxycarbonyl or        carbonyl,    -   R³ is straight-chain or branched C₁-C₁₈-alkyl or C₆-C₁₀-aryl,    -   R⁴ is an R³ radical or is a radical of the formulae        -   q is from 20 to 100,        -   q1 and q2 are each independently from 20 to 100        -   where the sum of q1+q2=q,        -   q3, q4, q5 and q6 are each independently from 20 to 100        -   where the sum of q3+q4+q5+q6=q,        -   r is from 0to 20,        -   r1 and r2 are each independently from 0 to 20        -   where the sum of r1+r2=r,        -   r3, r4, r5 and r6 are each independently from 0 to 20        -   where the sum of r3+r4+r5+r6=r, and        -   the ratio of r:q≦0.25,        -   m is from 1 to 7,        -   m7 and m8 are each independently from 1 to 7        -   where 2≦m7+m8 and        -   the ratio of q:m≧4,        -   s is from 5 to 100, preferably from 15 to 100        -   t is from 5 to 100, preferably from 5 to 20        -   where t:s≦0.25,        -   0≦z1≦2000,        -   0≦z2≦2000,        -   at least one R4≠R3,        -   and    -   for the formula (9′):        0.01≦Σ alkyl radicals R³:Σ q≦0.5.

The compounds (a) are more preferably those of the formulae (1) to (9)where

-   -   E is H—, CH₃—, CH₃CH₂—, CH₃CH₂CH₂—, (CH₃)₂CH—, CH₃CH₂CH₂CH₂— or        CH₃C(O)—    -   R¹ is a radical of the formulae        -   where        -   n1=from 9 to 23,        -   n2=from 3 to 23,        -   n3=from 0 to 18,        -   n4=from 7 to 23,        -   n5=from 3 to 15,    -   R² is a radical of the formulae        -   where        -   n6=8to to 28,    -   R³ is C₁-C₁₈-alkyl or C₆-C₁₀-aryl,    -   R⁴ is an R³ radical or is a radical of the formulae        —CH₂CH₂—O—[CH₂CH₂O]_(q)—[CH₂CH(CH₃)O]_(r)-E,        -   or            —CH₂CH₂CH₂—O—[CH₂CH₂O]_(q)—[CH₂CH(CH₃)O]_(r)-E        -   q is from 25 to 60,        -   q1 and q2 are each independently from 25 to 60        -   q3, q4, q5 and q6 are each independently from 25 to 60        -   where the sum of q3+q4+q5+q6=q,        -   r is from 0 to 10,        -   r1 and r2 are each independently from 0 to 10        -   where the sum of r1+r2=r,        -   r3, r4, r5 and r6 are each independently from 0 to 10,        -   where the sum of r3+r4+r5+r6=r, and        -   the ratio of r:q≦0.25, and        -   0.01≦Σ alkyl radicals R³:Σ q+r <0.1.

The compounds (a) are more preferably also those of the formulae (1′) to(9′) where

-   -   E is H—, CH₃—, CH₃CH₂—, CH₃CH₂CH₂—, (CH₃)₂CH—, CH₃CH₂CH₂CH₂— or        CH₃C(O)—    -   R¹ is a radical of the formulae        -   where        -   n1=from 9 to 23,        -   n2=from 3 to 23, preferably from 6 to 23        -   n3=from 0 to 18, where, preferably, n2+n3≦31,        -   n4=from 7 to 23,        -   n5=from 3 to to 15,    -   R² is a radical of the formulae        -   where        -   n6=8to to 28,    -   R³ is C₁-C₁₈-alkyl or C₆-C₁₀-aryl,    -   R⁴ is an R³ radical or is a radical of the formulae        -   q is from 25 to 60,        -   q1 and q2 are each independently from 25 to 60        -   q3, q4, q5 and q6 are each independently from 25 to 60        -   where the sum of q3+q4+q5+q6=q,        -   r is from 0 to 10,        -   r1 and r2 are each independently from 0 to 10        -   where the sum of r1+r2=r,        -   r3, r4, r5 and r6 are each independently from 0 to 10        -   where the sum of r3+r4+r5+r6=r, and        -   the ratio of r:q≦0.25, and        -   for the formula (9′):            0.01≦Σ alkyl radicals R³:Σ q≦0.1.

Very particular preference is given to inventive formulations whichcomprise, as compound (a), the ester of stearic acid and 40 mol of EO.

The inventive formulations comprise at least one aminoalkylsiloxanecompound quaternized on the nitrogen (silicone quat). Such compounds andtheir preparation are known, for example, from WO 02/10 256, WO 02/10257, WO 02/10 259, EP 282 720, EP 17 121, DE-A 100 36 533, DE-A 100 36539, DE-A 100 36 532, DE-A 100 36 522 and DE -A 102 12 470.

The quaternized aminoalkylsiloxane compounds present in the inventiveformulations preferably correspond to linear or cyclic polysiloxanepolymers of WO 02-10259 having repeating essential structural units ofthe formulae (10) and (11)

-   -   where    -   X is a divalent hydrocarbon radical having at least 4 carbon        atoms which may have a hydroxyl group, preferably has a hydroxyl        group, and which may be interrupted by one oxygen atom, and the        X groups in the repeating units may be the same or different,    -   Y is a divalent hydrocarbon radical having at least 2 carbon        atoms which has a hydroxyl group and which may be interrupted by        one or more oxygen or nitrogen atoms,    -   R¹¹, R¹², R¹³ and R¹⁴ are the same or different and are each        alkyl radicals having from 1 to 4 carbon atoms or benzyl        radicals, or the R¹¹ and R¹³ or R¹² and R¹⁴ radicals may in each        case be constituents of a bridging alkylene radical,    -   R¹⁶ is H or an alkyl radical having from 1 to 20 carbon atoms        which may be oxygen-substituted,    -   M is the structure —B—O-(EOx)_(v)(POx)_(w)-B—, where        -   EOx is an ethylene oxide unit and POx is a propylene oxide            unit,    -   B is straight-chain or branched C₂-C₆-alkylene,    -   v is from 0 to 200,    -   w is from 0 to 200,        v+w≧1,    -   n is from 2 to 1000 where the n in the repeating units may be        the same or different,    -   A- is an inorganic or organic anion.

The inventive formulations in some cases also comprise any mixtures ofthe above-designated quaternized aminoalkylsiloxane compounds with thecorresponding nonquaternized compounds. In these nonquaternizedcompounds, in each case one of the R¹¹ or R¹² radicals or R¹³or R¹⁴radicals in the main chain on the nitrogen atoms in the formula (10) isthus absent.

The quaternized aminoalkylsiloxane compounds which are preferred inaccordance with the invention form part of the subject-matter of WO02/10 259 and are described there generally and specifically. Thecontents of WO 02/10 259 are incorporated fully by the presentapplication.

In a preferred embodiment of the invention, the amounts of hydrophilic,nonionogenic, interface-active compounds (a) and/or hydrophilicdispersants (b) and/or salts (c) to the amounts of quaternizedaminoalkylsiloxane compounds are in a weight ratio Ω of Ω=0.05 to 10,preferably Ω=0.05 to 5, especially Q =0.05 to 3, very especially Ω=0.05to 1. Ω illustrates only the ratio of total amount of component (a) to(c) to amount of silicone quat. When the amounts of additive (a) and/or(b) and/or (c) are too small, the effective stabilization in the fiberfinishing is exhausted, i.e., for example, that the shear stabilityunder some circumstances cannot always be maintained under strongmechanical shear, high temperatures, long finishing cycles. Very largeadditive amounts are uneconomic and can change the hand of the textilein an undesired manner.

The additives a) to c) described may be added in two ways. It ispossible firstly to introduce the inventive additives directly into theformulations. Secondly, it may be favorable under practice conditions tofirst dilute the formulations to use concentration and to subsequentlyadd the inventive additives to the liquor prepared.

In addition to components (a) and/or (b) and/or (c), the inventiveformulations may also comprise further interface-active components (f)which enable emulsification or microemulsification.

These components (f) are customary formulation agents, known to thoseskilled in the art, for preparing the silicone (micro)emulsions which,however, alone are not stable against high energy input. Such preferredcomponents f1) to f6) include: (f1) oxalkylation products which areobtainable by alkoxylating, with ethylene oxide or propylene oxide,condensation products of phenolic OH-containing aromatics withformaldehyde and NH functional groups. f2) nonionic or ionicallymodified compounds from the group of the alkoxylates, alkylolamides,esters, amine oxides and alkylpolyglycosides, especially reactionproducts of alkylene oxides with alkylatable compounds, for examplefatty alcohols, fatty amines, fatty acids, phenols, alkylphenols,carboxamides and resin acids. They are, for example, ethylene oxideethers from the class of the reaction products of ethylene oxide withsaturated and/or unsaturated fatty alcohols having from 6 to 25 carbonatoms (commercially available, for example, in the form of Renex®product series) or alkylphenols having from 4 to 12 carbon atoms in thealkyl radical or saturated and/or unsaturated fatty amines having from14 to 20 carbon atoms or saturated and/or unsaturated fatty acids havingfrom 14 to 22 carbon atoms, or esterification and/or arylation productswhich are prepared from natural or modified, optionally hydrogenatedcastor oil fatty substances and are optionally joined to give repeatingunits by esterification with dicarboxylic acids. f3) ionic or nonioniccompounds from the group of the reaction products of alkylene oxide withsorbitan esters [Tween, ICI], oxalkylated acety-lenediols and glycols,oxalkylated phenols, especially phenol/styrene polyglycol ethers. f4)ionic or nonionic polymeric surface-active agents from the group of thehomo- and copolymers, graft polymers and graft copolymers and random andlinear block copolymers. f5) anionic surface-active agents, for examplealkyl sulfates, ether sulfates, ether carboxylates, phosphate esters,sulfosuccinamides, paraffin sulfonates, olefin sulfonates, sarcosinates,isothionates and taurates. f6) amphoteric surface-active agents such asbetaines and ampholytes especially glycinates, propionates andimidazolines.

Particularly preferred formulation constituents (f) are alkoxylatedfatty alcohols, branched fatty alcohols and fatty acids having from 4 to14 alkoxy units; very particularly preferred formulation constituents(f) are alkoxylated fatty alcohols, branched fatty alcohols having from6 to 12 alkoxyl units, especially formulations which contain the etherof tridecyl alcohol with 12 mol of EO, the ether of tridecyl alcoholwith 6 mol of EO.

The formulation constituents are generally added in customary amounts tothe inventive formulation. Preference is given to adding the components(f) in amounts of from 1 to 200% by weight, preferably from 10 to 80% byweight, more preferably 10-50% by weight, based on the quaternizedaminoalkylsiloxane.

In addition to component(s) (a) to (c), the formulations, in each casealone or in combination, and the additives (f) may also comprise furtherassistants in the amounts customary for these assistants.

Typical assistants in the context of the invention include levelingagents, wetting agents, lustering agents, fiber protection agents,antislip agents and further prior art assistants. A good overview of theinventive assistants can be found in Chwala/Anger, Handbuch derTextilhilfsmittel, Verlag Chemie, Weinhein 1977.

Furthermore, buffer systems may be used to obtain an optimal pH valueduring the finishing.

To prepare the inventive formulations, the quaternizedaminoalkylsiloxane compounds may be mixed with components (a), (b)and/or (c), optionally with addition of further, abovementionedconstituents, preferably within a temperature range of from 20 to 90°C., more preferably of from 25 to 70° C., most preferably from 30 to 60°C.

The quaternized aminoalkylsiloxanes are preferably added to thecompound(s) (a), (b) and/or (c), particular preference is given toinitially charging the quaternized aminoalkylsiloxane (silicone quat)and completing the emulsion formulation by adding the compound(s) (a),(b) and/or (c) and optionally further additives.

The inventive formulations are outstandingly suitable as textilesofteners in the finishing of textile structures, especially those madeof cotton, keratin fibers, preferably wool, silk or synthetic fibers or,for example, used very efficiently for the finishing of textilestructures made of mixtures of cotton with polyester, polyamide,polyacrylonitrile, wool or silk. Excellent results are equally achievedin the finishing of textile structures made of synthetic fibers,especially made of polyester, polyamide, polypropylene or mixturesthereof.

Textile structures are preferably wovens, knits, including formed-loopknits, and nonwovens.

It has been found that the inventive formulations are particularlyadvantageous for the finishing of cotton or cotton-containing textileswhich have been pretreated with anionic lighteners by the jet process.

When the inventive formulations are used, it is possible not only toachieve outstanding softener results but also an improvement in otherproperties of the textile such as the solubility or an increase in thegloss.

The finishing is generally effected by the continuous process (padmangle or backwasher process) or by the exhaustion process (jetprocess). When the inventive formulations are employed by one of thesefinishing processes, it has been found to be advantageous to maintainthe following technological parameters:

Continuous (for Example Pad Mangle, Backwasher)

1. At 11% silicone concentration: 5-50 g/l, preferably 10-40 g/l andespecially 10-25 g/l of SQ (=silicone quat) formulation+a) to c)

2. Finishing temperature: Room temperature

3. Drying temperature: 75-105° C. in a forced-air drying cabinet or10-60 sec on a tenter frame at 150° C., particularly 30-45 sec

4. Time in the forced-air drying cabinet: 10-20 minutes

Exhaustion Process (for Example Jet, Winchbeck)

1. At 11% silicone concentration: 1.0-5.0%, preferably 1.5-3.5% andespecially 1.5-2.5%

2. Finishing temperature: 30-60° C., preferably 35-50° C. and especially35-45° C.

3. Heating rate: 2-4° C./minute

4. Finishing time: 15-25 minutes

5. Liquor ratio: from 1:5 to 1:50, particularly from 1:10 to 1:30

6. Drying temperature 75-105° C. in a forced-air drying cabinet or 10-60sec on a tenter frame at 150° C., particularly 30-45 sec

7. Time in the forced-air drying cabinet:10-20 minutes

EXAMPLES

In the formulations which follow, a silicone quat (SQ) synthesizedaccording to WO 02/10259, Example 1, was used which had the followingstructural elements and is prepared as follows:

1a) A 1 liter three-neck flask was initially charged at room temperaturewith 24 g of water and 4.18 g (0.048 mol of tertiary amino groups) ofN,N,N′,N′-tetramethyl-1,6-hexanediamine and 3.8 g (0.012 mol of primaryamino groups) of an alkylene oxide derivative, obtainable under thetrade name Jeffamin® ED 600, of the structureH₂NCH(CH₃)CH₂[OCH₂CH(CH₃)]_(a)(OCH₂CH₂)₉ [OCH₂CH(CH₃)]_(b)NH₂

where a+b=3.6.

Within 5 minutes, 12.0 g (0.03 mol) of dodecanoic acid in the form of a50% solution in 2-propanol and 1.8 g (0.03 mol) of acetic acid wereadded. After the mixture had been heated to 50° C., 194.1 g (0.06 mol ofepoxy groups) of an epoxy siloxane of the average composition

and 30 ml of 2-propanol were added dropwise within 30 minutes. Theyellow, opaque mixture was heated to reflux temperature for 6 hours.After removal of all constituents volatile up to 100° C. and at areduced pressure of 2 mmHg, 204 g of a slightly yellow, opaque materialwere obtained which contains the following structural elements

Starting from this silicone material, three microemulsion concentratesof the following composition were prepared: Formulation 1 (F1)Formulation 2 (F2) Formulation 3 (F3) 430 g SQ 430 g SQ 430 g SQ 258 gRenex ® 36 125 g Renex ® 36 125 g Renex ® 36 44.5 g Renex ® 30 44.5 gRenex ® 30 44.5 g Renex ® 30 10 g acetic acid 10 g acetic acid 10 gacetic acid 7.5 g sodium acetate 7.5 g sodium acetate 7.5 g sodiumacetate 245 g dist. water 245 g dist. water 245 g dist. water 79.5 g2-Propanol 79.5 g 2-Propanol 87.5 g Crodet S40 59 g Crodet ® S40

These three microemulsion concentrates (about 40% based on SQ) arediluted uniformly with water to 11% silicone quat content in each case.Of these 11% transparent microemulsions, in each case 6 g (absoluteamount of silicone quat 0.66 g) are withdrawn, mixed intensively with6000 ml of water and optionally additives and utilized for jet finishingunder the following boundary conditions:

Jet type: Mathis Labor-Jumbo-Jet

Jet pump: Level 6 (highest possible shear)

Amount of water in the jet: 6000 ml

Finishing: 15 minutes at 40° C.

Drying: 80° C.

Textile: 300 g bleached and with optical brightener (e.g. Blankophor® BAtreated cotton pullover).

The following table summarizes the results of the finishing experiments.Hand Foam height Silicone after Hydrophi- in the jet No. Formul.Additive deposition* drying** licity*** in cm 1 F1 high deposits, ok ok12-13 tacky 2 F1 0.39 g Renex ® 36 high deposits, ok ok 12-13 0.06 gRenex ®30 tacky 3 F1 0.5 g Al₂(SO₄)₃.16H₂O no deposits, ok ok 5-6 fewdefects 4 F1 0.05 g Al₂(SO₄)₃.16H₂O no deposits, ok ok 5-6 3 g MgCl₂x6H₂O few defects 5 F2 no deposits, ok ok 6-7 no defects 6 F3 0.02 gCrodet ® S40 no deposits, ok ok 6-7 no defects 7 F1 0.18 g Crodet ® S40no deposits, ok ok 6-7 no defects*Deposits on glass and steel parts of the jet**Having a silicone-like softness with volume increase***Drop absorption time ≦3 secondsRenex ® 36, trade name of ICI surfactants; tridecyl alcohol-(EO)₁₂—OHRenex ® 30, trade name of ICI surfactants; tridecyl alcohol-(EO)₆—OHCrodet ® S40, trade name of Croda GmbH; stearic acid-(EO)₄₀—OH

Experiment 1 describes the unacceptable result of a noninventive priorart experiment. Doubling of the amount of both Renex surfactants doesnot lead to prevention of deposits (Experiment 2, noninventive).

Experiments 3 and 4 demonstrate that an inventive addition of salts ofpolyvalent cations can reliably prevent deposits. Aluminum salts aremore effective than magnesium compounds.

Experiment 5 shows that an inventive incorporation of hydrophilicinterface-active compounds directly into the formulation reliablyprevents deposits. It is also true of a likewise inventive partialsubsequent addition (Experiment 6) or inventive full addition(Experiment 7) of this hydrophilic interface-active compound.

1. A formulation comprising at least one quaternized aminoalkylsiloxaneand at least one compound from the group of a) the hydrophilic,nonionogenic, interface-active compounds, b) the hydrophilic dispersantsand c) the salts of di- or trivalent metals with inorganic acids.
 2. Theformulation as claimed in claim 1, characterized in that thehydrophilic, nonionogenic, interface-active compounds (a) are compoundsmodified with ethylene/propylene oxide (EO/PO), optionally unsaturatedand/or branched, from the group of the fatty alcohols, fatty acids,alcohols, acids, alkylaryl derivatives, fatty amines, glycerides andsorbitan esters, in each of which the number of EO/PO units is between15 and 150, the ratio of PO units to EO units being equal to or lowerthan 0.25, and in which the number of ethylene oxide units (EO fraction)is greater than or equal to the number of carbon atoms in the non-EOfraction, or are alkylpolyglycosides, ethylene oxide/propylene oxidecopolymers and polyethersiloxanes.
 3. The formulation as claimed in atleast one of claims 1 and 2, characterized in that the hydrophilicdispersants (b) are water-soluble polysaccharides from the group of thesubstituted celluloses.
 4. The formulation as claimed in at least one ofclaims 1 to 3, characterized in that the salts (c) are those of themetals calcium, magnesium and aluminum with hydrochloric acid, sulfuricacid or phosphoric acid, and the salts may also be present in the formof their hydrates.
 5. The formulation as claimed in at least one ofclaims 1 to 4, characterized in that compound (a) is a compound of theformulae (1) to (9)

where E is an R¹ radical, hydrogen, straight-chain or branched,saturated or mono- or polyunsaturated C₁-C₁₈-alkyl which is optionallymono- or polysubstituted by —OH, C₁-C₄-alkoxy, C₁-C₄-alkoxycarbonyl orcarbonyl, or is C₅-C₁₀-cycloalkyl which is optionally mono- orpolysubstituted by C₁-C₄-alkyl, —OH, C₁-C₄-alkoxy, C₁-C₄-alkoxycarbonylor carbonyl R¹ is straight-chain or branched, saturated or unsaturatedC₈-C₄₀-alkyl whose alkyl chain is optionally interrupted singly ormultiply by oxygen and/or nitrogen atoms and which is optionally mono-or polysubstituted by —OH, C₁-C₄-alkoxy, C₁-C₄-alkoxycarbonyl orcarbonyl, amino, mono- or di-C₁-C₄-alkylamino, or is C₅-C₁₀-cycloalkylwhose alkyl chain is optionally singly or multiply by oxygen mono- orpolysubstituted by C₁-C₄-alkyl, —OH, C₁-C₄-alkoxy, C₁-C₄-alkoxycarbonylor carbonyl, amino, mono- or di-C₁-C₄-alkyl-amino, R² is straight-chainor branched, saturated or mono- to polyunsaturated C₈-C₄₀-alkyl which isoptionally mono- or polysubstituted by —OH, C₁-C₄-alkoxy,C₁-C₄-alkoxycarbonyl or carbonyl, R³ is straight-chain or branchedC₁-C₂₆-alkyl or C₆-C₁₀-aryl, R⁴ is R³ or a radical of the formulae—CH₂CH₂—O—[CH₂CH₂O]_(q)—[CH₂CH(CH₃)O]_(r)-E,—CH₂CH₂CH₂—O—[CH₂CH₂O]_(q)—[CH₂CH(CH₃)O]_(r)-E—CH₂CH₂CH₂—O—CH₂CHOHCH₂—O—[CH₂CH₂O]_(q)—[CH₂CH(CH₃)O]_(r)-E—Z—[CH₂CH₂O]_(q)—[CH₂CH(CH₃)O]_(r)-E where Z is a straight-chain orbranched alkyl or cycloalkyl radical which is in each case interruptedby —O— and/or —CO— and may optionally be substituted by at least one OHgroup, or

q is from 15 to 150, q1 and q2 are each independently from 0 to 150where the sum of q1+q2=q, q3, q4, q5 and q6 are each independently from0 to 150 where the sum of q3+q4+q5+q6=q, r is from 0 to 50, r1 and r2are each independently from 0 to 50 where the sum of r1+r2=r, r3, r4, r5and r6 are each independently from 0 to 50 where the sum ofr3+r4+r5+r6=r, and the ratio of r:q≦0.25; m is from 1 to 50, m7 and m8are each independently from 1 to 50 where 2≦m7+m8 and the sum ofm7+m8=m+1, and the ratio of q:m≧4, s is from 5 to 150, t is from 5 to150 where 0.05≦s:t≦20, 0≦z1≦2000, 0<z2≦2000, at least one R4≠R3, and0.01≦Σ alkyl radicals R³:Σ q+r≦1.
 6. The formulation as claimed in atleast one of claims 1 to 5, characterized in that compound (a) is acompound of the formulae (1) to (9) as claimed in claim 5, where E ishydrogen, straight-chain or branched, saturated or mono- orpolyunsaturated C₁-C₄-alkyl which is optionally mono- to disubstitutedby —OH, C₁-C₄-alkoxy, C₁-C₄-alkoxycarbonyl or carbonyl, or is C₅-C₆-cycloalkyl which is in each case optionally mono- or polysubstituted byC₁-C₄-alkyl, —OH, C₁-C₄-alkoxy, C₁-C₄-alkoxycarbonyl or carbonyl, R¹ isstraight-chain or branched, saturated or unsaturated C₁₀-C₃₆-alkyl whosealkyl chain is optionally interrupted singly or multiply by oxygenand/or nitrogen atoms and which is optionally mono- or polysubstitutedby —OH, C₁-C₄-alkoxy, C₁-C₄-alkoxycarbonyl or carbonyl, amino, mono- ordi-C₁-C₄-alkylamino, or is C₅-C₆-cycloalkyl whose alkyl chain isoptionally interrupted singly or multiply by oxygen and/or nitrogenatoms and which is optionally mono- or polysubstituted by C₁-C₄-alkyl,—OH, C₁-C₄-alkoxy, C_(l)-C₄-alkoxycarbonyl or carbonyl, amino, mono- ordi-C₁-C₄-alkylamino, R² is straight-chain or branched, saturated ormono- to polyunsaturated C₁₀-C₃₆-alkyl which is optionally mono- orpolysubstituted by —OH, C₁-C₄-alkoxy, C₁-C₄-alkoxycarbonyl or carbonyl,R³ is straight-chain or branched C₁-C₁₈-alkyl or C₆-C₁₀-aryl, R⁴ is anR³ radical or is a radical of the formulae—CH₂CH₂—O—[CH₂CH₂O]_(q)—[CH₂CH(CH₃)O]_(r)-E,or—CH₂CH₂CH₂—O—[CH₂CH₂O]_(q)—[CH₂CH(CH₃)O]_(r)E, q1 and q2 are eachindependently from 20 to 100 where the sum of q1+q2=q, q3, q4, q5 and q6are each independently from 20 to 100 where the sum of q3+q4+q5+q6=q, ris from 0 to 20, r1 and r2 are each independently from 0 to 20 where thesum of r1+r2=r, r3, r4, r5 and r6 are each independently from 0 to 20where the sum of r3+r4+r5+r6=r, and the ratio of r:q≦0.25, m is from 1to 7, m7 and m8 are each independently from 1 to 7 where 2≦m7+m8 and thesum of m7+m8=m, and the ratio of q:m≧4, s is from 5 to 100, t is from 5to 100 where 0.05≦s:t≦20, 0≦z1≦2000, 0≦z2≦2000, at least one R4≠R3, and0.01≦Σ alkyl radicals R³:Σ q+r≦0.5.
 7. The formulation as claimed in atleast one of claims 1 to 4, characterized in that compound (a) is acompound of the formulae (1′) to (9′)

where the brackets “{” and “}” shown in formulae (1′)-(8′) ethyleneoxide or propylene oxide units may either be arranged blockwise as shownor else be in any random distribution, E is an R¹ radical, hydrogen,straight-chain or branched, saturated or mono- or polyunsaturatedC₁-C₁₈-alkyl which is optionally mono- or polysubstituted by —OH,C₁-C₄-alkoxy, C₁-C₄-alkoxycarbonyl or carbonyl, or is C₅-C₁₀-cycloalkylwhich is optionally mono- or polysubstituted by C₁-C₄-alkyl, —OH,C₁-C₄-alkoxy, C₁-C₄-alkoxycarbonyl or carbonyl, R¹ is straight-chain orbranched, saturated or unsaturated C₈-C₄₀-alkyl whose alkyl chain isoptionally interrupted singly or multiply by oxygen and/or nitrogenatoms and which is optionally mono- or polysubstituted by —OH,C₁-C₄-alkoxy, C₁-C₄-alkoxycarbonyl or carbonyl, amino, mono- ordi-C₁-C₄-alkylamino, or is C₅-C₁₀-cycloalkyl whose alkyl chain isoptionally interrupted singly or multiply by oxygen and/or nitrogenatoms and which is optionally mono- or polysubstituted by C₁-C₄-alkyl,—OH, C₁-C₄-alkoxy, C_(l)-C₄-alkoxycarbonyl or carbonyl, amino, mono- ordi-C₁-C₄-alkylamino, or is C₆-C₁₀-aryl which is optionally substituted,especially by C₃-C₁₅-alkoxycarbonyl alkyl, R² is straight-chain orbranched, saturated or mono- to polyunsaturated C₈-C₄₀-alkyl which isoptionally mono- or polysubstituted by —OH, C₁-C₄-alkoxy,C₁-C₄-alkoxycarbonyl or carbonyl, R³ is straight-chain or branchedC₁-C₂₆-alkyl or C₆-C₁₀-aryl, R⁴ is R³ or is a radical of the formulae

where Z is a straight-chain or branched alkyl or cycloalkyl radicalwhich is in each case interrupted by —O— and /or —CO— and may optionallybe substituted by at least one OH group or

q is from 15 to 150, q1 and q2 are each independently from 0 to 150where the sum of q1+q2=q, q3, q4, q5 and q6 are each independently from0 to 150 where the sum of q3+q4+q5+q6=q, r is from 0 to 50, r1 and r2are each independently from 0 to 50 where the sum of r1+r2=r, r3, r4, r5and r6 are each independently from 0 to 50 where the sum ofr3+r4+r5+r6=r, and the ratio of r:q≦0.25, m is from 1 to 50, m7 and m8are each independently from 1 to 50 where 2≦m7+m8, and the ratio ofq:m≧4, s is from 5 to 150, preferably 15-150, t is from 5 to 150,preferably from 5 to 150 and in particular from 5 to 20, 0≦z1≦2000,0≦z2≦2000, at least one R4≠R3, and for formula (9′):0.01≦Σ alkyl radicals R³ :Σ q+r≦1.
 8. The formulation as claimed in atleast one of claims 1 to 4 or 7, characterized in that compound (a) is acompound of the formulae (1′) to (9′) as claimed in claim 7, where E ishydrogen, straight-chain or branched, saturated or mono- orpolyunsaturated C₁-C₄-alkyl which is optionally mono- to disubstitutedby —OH, C₁-C₄-alkoxy, C₁-C₄-alkoxycarbonyl or carbonyl, or is C₅-C₆-cycloalkyl which is in each case optionally mono- or polysubstituted byC₁-C₄-alkyl, —OH, C₁-C₄-alkoxy, C₁-C₄-alkoxycarbonyl or carbonyl, R¹ isstraight-chain or branched, saturated or unsaturated C₁₀-C₃₆-alkyl whosealkyl chain is optionally interrupted singly or multiply by oxygenand/or nitrogen atoms and which is optionally mono- or polysubstitutedby —OH, C₁-C₄-alkoxy, C₁-C₄-alkoxycarbonyl or carbonyl, amino, mono- ordi-C₁-C₄-alkylamino, or is C₅-C₆-cycloalkyl whose alkyl chain isoptionally interrupted singly or multiply by oxygen and/or nitrogenatoms and which is optionally singly or multiply by C₁-C₄-alkyl, —OH,C₁-C₄-alkoxy, C₁-C₄-alkoxycarbonyl, or is C₆-C₁₀-aryl which isoptionally substituted, especially by C₃-C₁₅-alkyl, R² is straight-chainor branched, saturated or mono- to polyunsaturated C₁₀-C₃₆-alkyl whichis optionally mono- or polysubstituted by —OH, C₁-C₄-alkoxy,C₁-C₄-alkoxycarbonyl or carbonyl, R³ is straight-chain or branchedC₁-C₁₈-alkyl or C₆-C₁₀-aryl, R⁴ is an R³ radical or is a radical of theformulae

q is from 20 to 100, q1 and q2 are each independently from 20 to 100where the sum of q1+q2=q, q3, q4, q5 and q6 are each independently from20 to 100 where the sum of q3+q4+q5+q6=q, r1 and r2 are eachindependently from 0 to 20 where the sum of r1+r2=r, r3, r4, r5 and r6are each independently from 0 to 20 where the sum of r3+r4+r5+r6=r, andthe ratio of r:q≦0.25, m is from 1 to 7, m7 and m8 are eachindependently from 1 to 7 where 2≦m7+m8, and the ratio of q:m≧4, s isfrom 5 to 100, preferably from 15 to 100 t is from 5 to 100, preferablyfrom 5 to 20 where t:s≦0.25, 0≦z1≦2000, 0≦z2≦2000, at least one R4≠R3,and for the formula (9′):0.01≦Σ alkyl radicals R³:Σ q≦0.5.
 9. The formulation as claimed in atleast one of claims 1 to 6, characterized in that compound (a)corresponds to the formulae (1) to (9) as claimed in claim 5, where E isH, CH₃—, CH₃CH₂—, CH₃CH₂CH₂—, (CH₃)₂CH—, CH₃CH₂CH₂CH₂— or CH₃C(O)—, R¹is a radical of the formulae

where n1=from 9 to 23, n2=from 3 to 23, n3=from 0 to 18, n4=from 7 to23, n5=from 3 to to 15, R² is a radical of the formulae

where n6=8 to to 28, R³ is C₁-C₁₈-alkyl or C₆-C₁₀-aryl, R⁴ is an R³radical or is a radical of the formulae—CH₂CH₂—O—[CH₂CH₂O]_(q)—[CH₂CH(CH₃)O]_(r)-E,or—CH₂CH₂CH₂—O—[CH₂CH₂O]_(q)—[CH₂CH(CH₃)O]_(r)-E q is from 25 to 60, q1and q2 are each independently from 25 to 60 where the sum of q1+q2=q,q3, q4, q5 and q6 are each independently from 25 to 60 where the sum ofq3+q4+q5+q6=q, r is from 0 to 10, r1 and r2 are each independently from0 to 10 where the sum of r1+r2=r, r3, r4, r5 and r6 are eachindependently from 0 to 10, the ratio of r:q≦0.25, and for the formula(9):0.01≦Σ alkyl radicals R ³ :Σ q+r≦0.1.
 10. The formulation as claimed inat least one of claims 1 to 4 and 7 to 8, characterized in that compound(a) corresponds to the formulae (1′) to (9′) as claimed in claim 7,where E is H, CH₃—, CH₃CH₂—, CH₃CH₂CH₂—, (CH₃)₂CH—, CH₃CH₂CH₂CH₂— orCH₃C(O)— R¹ is a radical of the formulae

n1=from 9 to 23, n2=from 3 to 23, preferably from 6 to 23 n3=from 0 to18, where, preferably, n2+n3≦31, n4=from 7 to 23, n5=from 3 to to 15, R²is a radical of the formulae

where n6=8 to to 28, R³ is C₁-C₁₈-alkyl or C₆-C₁₀-aryl, R⁴ is an R³radical or is a radical of the formulae

q is from 25 to 60, q1 and q2 are each independently from 25 to 60 wherethe sum of q1+q2=q, q3, q4, q5 and q6 are each independently from 25 to60 where the sum of q3+q4+q5+q6=q, r is from 0 to 10, r1 and r2 are eachindependently from 0 to 10 where the sum of r1+r2=r, r3, r4, r5 and r6are each independently from 0 to 10, where the sum of r3+r4+r5+r6=r, andfor the formula (9′):0.01≦Σ alkyl radicals R ³ :Σ q≦0.1.
 11. The formulation as claimed in atleast one of claims 1 to 10, characterized in that the compounds (b) arecarboxymethylcellulose, hydroxyethylcellulose,methylhydroxypropylcellulose or a compound of the formula

where x is from 1.5 to 20, preferably from 1.5 to
 10. 12. Theformulation as claimed in at least one of claims 1 to 11, characterizedin that the quaternized aminoalkylsiloxanes are linear or cyclicpolysiloxane polymers having repeating structural units of the formulae(10) and (11)

where X is a divalent hydrocarbon radical having at least 4 carbon atomswhich may have a hydroxyl group, preferably has a hydroxyl group, andwhich may be interrupted by one oxygen atom, and the X groups in therepeating units may the same or different, Y is a divalent hydrocarbonradical having at least 2 carbon atoms which has a hydroxyl group andwhich may be interrupted by one or more oxygen or nitrogen atoms, R¹¹,R¹², R¹³ and R¹⁴ are the same or different and are each alkyl radicalshaving from 1 to 4 carbon atoms or benzyl radicals, or the R¹ and R³ orR² and R⁴ radicals may in each case be constituents of a bridgingalkylene radical, R¹⁶ is H or an alkyl radical having from 1 to 20carbon atoms which may be oxygen-substituted, M is the structure—B—O-(EOx)_(v)(POx)_(w)-B—, where EOx is an ethylene oxide unit and POxis a propylene oxide unit, B is straight-chain or branchedC₂-C₆-alkylene, v is from 0 to 200, w is from 0 to 200,v+w≧1, n is from 2 to 1000 where the n in the repeating units may be thesame or different, A⁻ is an inorganic or organic anion.
 13. Theformulation as claimed in at least one of claims 1 to 12, comprising atleast one quaternized aminoallcylsiloxane and at least one compound fromthe group of the hydrophilic, nonionogenic, interface-active compounds(a).
 14. The formulation as claimed in at least one of claims 1 to 13,characterized in that the compound (a) present is the ester of stearicacid and 40 mol of EO.
 15. The formulation as claimed in at least one ofclaims 1 to 14, characterized in that, as a further component, at leastone compound (f) from the group of the interface-active compounds andemulsifiers is present.
 16. The formulation as claimed in claim 15,characterized in that, as interface-active substances f) the ether oftridecyl alcohol with 12 mol of EO and the ether of tridecyl alcoholwith 6 mol of EO are present.
 17. The formulation as claimed in at leastone of claims 1 to 16, characterized in that the amounts of hydrophilic,nonionogenic, interface-active compounds (a) and/or hydrophilicdispersants (b) and/or salts (c) to the amounts of quaternizedaminoalkylsiloxane compounds are in a ratio Ω of Ω=0.05 to
 10. 18. Theuse of the formulation as claimed in at least one of claims 1 to 17 as atextile softener in the finishing of textile structures by thecontinuous or exhaust process.
 19. The use as claimed in claim 18 forthe finishing of textile structures made of cotton, keratin fibers,preferably wool, silk, synthetic fibers or mixtures of theaforementioned types.
 20. The use as claimed in claim 18 for thefinishing of textile structures made of mixtures of cotton withpolyester, polyamide, polyacrylonitrile, wool or silk.
 21. The use asclaimed in claim 18 for the finishing of textile structures made ofpolyester, polyamide, polypropylene or mixtures thereof.
 22. The use asclaimed in at least one of claims 19 to 20, characterized in thattextile structures made of cotton or of mixtures of cotton withpolyester, polyamide, polyacrylonitrile, wool or silk, said textilestructures having been pretreated with anionic whiteners, are finishedin a jet dyeing apparatus.
 23. A process for preparing the formulationsas claimed in at least one of claims 1 to 17, characterized in that atleast one quaternized aminoalkylsiloxane is mixed with at least onecompound from the group of (a) the hydrophilic, nonionogenic,interface-active compounds, (b) the hydrophilic dispersants and thesalts of di- and trivalent metals with inorganic acids and optionallyfurther assistants and/or additives in the temperature range ofpreferably from 20 to 90° C.